WO2019069799A1 - Production method for polyamide-4 particles - Google Patents
Production method for polyamide-4 particles Download PDFInfo
- Publication number
- WO2019069799A1 WO2019069799A1 PCT/JP2018/036109 JP2018036109W WO2019069799A1 WO 2019069799 A1 WO2019069799 A1 WO 2019069799A1 JP 2018036109 W JP2018036109 W JP 2018036109W WO 2019069799 A1 WO2019069799 A1 WO 2019069799A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pyrrolidone
- particles
- polyamide
- aprotic solvent
- polymerization
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/24—Pyrrolidones or piperidones
Definitions
- the present invention relates to a method of producing polyamide 4 particles.
- Priority is claimed on Japanese Patent Application No. 2017-193534, filed Oct. 3, 2017, the content of which is incorporated herein by reference.
- the polyamide 4 particles are expected to be applied to cosmetics, adsorbents, carriers of catalysts, fibers and the like.
- a raw material mixture containing 2-pyrrolidone and / or 2-azetidinone as polymerization monomers and a basic polymerization catalyst is brought into contact with a compressible fluid containing carbon dioxide having a density of 450 kg / m 3 or more.
- a method for producing polyamide particles is described, which comprises melting or dissolving the raw material mixture and then ring-opening polymerizing the polymerization monomer.
- Patent Document 1 it is possible to produce polyamide particles having a d50 diameter of 10 ⁇ m to 1000 ⁇ m, a dispersion degree of 3.0 or less, and being porous.
- Patent Document 2 describes a method of polymerizing ⁇ -pyrrolidone in a saturated hydrocarbon in the presence of a higher fatty acid alkali salt in addition to a polymerization initiator and a catalyst. According to the method of Patent Document 2, it seems that uniform polymer particles having a diameter of about 0.05 to 2.0 mm can be produced.
- Patent Document 3 also describes the chemical formula for 2-pyrrolidone in the case of suspension polymerization of 2-pyrrolidone by the action of a basic polymerization catalyst and a carbon dioxide gas or sulfur dioxide of a polymerization initiator in an aprotic solvent.
- a process for producing a powdered 2-pyrrolidone polymer in which 0.1 to 5% by weight of the compound represented by (1) is present is described. (RCOO) 1/2 M (1) (Where R is a hydrocarbon group having 10 to 30 carbon atoms, and M is a divalent metal)
- Patent Document 1 The method described in Patent Document 1 is not suitable for industrial production because it requires special equipment. Further, the methods described in Patent Document 2 and Patent Document 3 are not suitable as a method for producing polyamide 4 particles having a smaller particle diameter because the particle diameter of the produced polyamide 4 particles tends to increase. .
- the present invention aims to provide a new method of producing polyamide 4 particles of small particle size.
- the inventors have found a method for producing polyamide 4 particles in which 2-pyrrolidone is polymerized in an organic solvent in the presence of a polymerization initiator and 2-pyrrolidone lithium salt, and the present invention has been completed.
- the present invention relates to the following inventions.
- polyamide 4 particles having a small particle size can be produced.
- the polyamide 4 particles are particles made of polyamide 4 obtained by polymerizing 2-pyrrolidone. Commercially available 2-pyrrolidone can be used.
- the volume average particle diameter of the polyamide 4 particles of the present invention is 1 ⁇ m to 100 ⁇ m, 1 ⁇ m to 80 ⁇ m, 1 ⁇ m to 70 ⁇ m, 1 ⁇ m to 60 ⁇ m, 1 ⁇ m to 50 ⁇ m, 1 ⁇ m to 40 ⁇ m, or 1 ⁇ m to 30 ⁇ m.
- the volume average particle diameter of the polyamide 4 particles of the present invention is obtained by ultrasonically dispersing a mixture of the produced polyamide 4 particles with water, and then using a laser diffraction / scattering type particle size distribution analyzer LA-920 (Horiba, Ltd.) Product).
- the CV (coefficient of variation) of the polyamide 4 particles of the present invention can be calculated by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
- CV (%) ((standard deviation) / (average particle size)) x 100
- the weight average molecular weight (Mw) of the polyamide 4 produced by the method of the present invention is not particularly limited, but 5,000 to 1,000,000, 10,000 to 1,000,000, 10,000 to 500,000. , 10,000 to 100,000, etc. can be selected. Further, the molecular weight distribution of the polyamide 4 produced by the method of the present invention is 1.0 to 6.0, 1.0 to 4.5, 1. in the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). 0 to 4.0, 1.0 to 3.5, 1.0 to 3.0 and the like can be selected.
- the weight average molecular weight and the number average molecular weight are values obtained by converting data measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent based on the molecular weight of standard polymethyl methacrylate.
- the polymerization is carried out in an aprotic solvent incompatible with 2-pyrrolidone.
- the aprotic solvent incompatible with 2-pyrrolidone is hexane, octane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, cyclohexane, decene, isoparaffin, liquid paraffin And aliphatic hydrocarbon solvents such as kerosene and petroleum ether. These solvents can be used singly or in combination of two or more.
- the aprotic solvent incompatible with 2-pyrrolidone of the present invention is a mixed solvent of an aprotic solvent compatible with 2-pyrrolidone and an aprotic solvent incompatible with 2-pyrrolidone, wherein It also includes mixed solvents incompatible with pyrrolidone.
- Examples of the aprotic solvent compatible with 2-pyrrolidone include toluene, cyclopentyl methyl ether, tetrahydrofuran and the like.
- the amount of the aprotic solvent used can be appropriately set according to the reaction scale and the like.
- 0.1 to 30 parts by weight, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight, 0.1 to 5 parts by weight of an aprotic solvent to 1 part by weight of 2-pyrrolidone It can be set in the range of 0.5 to 5 parts by weight or the like.
- Polymerization initiator As the polymerization initiator, known polymerization initiators used when polymerizing 2-pyrrolidone can be used. Specific examples of the polymerization initiator include carbon dioxide gas (CO 2 ); sulfur dioxide (SO 2 ); N-acetyl pyrrolidone, N-acetyl ⁇ -caprolactam, and other acylated compounds of lactams; acetyl chloride, stearoyl chloride, benzene -Carboxylic acid halides such as -1,3,5-tricarbonyl trichloride; Carboxylic acid anhydrides such as acetic anhydride and phthalic acid anhydride; Carboxylic acid esters such as carboxylic acid methyl ester; and Tolylene 2,4-diisocyanate An isocyanate compound, the reaction product of these polymerization initiators and a polymerization catalyst, etc.
- CO 2 carbon dioxide gas
- SO 2 sulfur dioxide
- polymerization initiators can be mentioned. These polymerization initiators can be used singly or in combination of two or more. The amount of the polymerization initiator used can be such as from 0.01 to 20 mol%, such as 0.1 to 10 mol%, based on the 2-pyrrolidone to be polymerized.
- (2-pyrrolidone lithium salt) In the production method of the present invention, polymerization of 2-pyrrolidone is carried out in the presence of lithium 2-pyrrolidone. Although the details are not clear, it is believed that 2-pyrrolidone lithium salt precipitates as a solid and this is adsorbed to the monomer / solvent interface to stabilize the suspended state.
- the 2-pyrrolidone lithium salt can be prepared by reacting 2-pyrrolidone with metal lithium, lithium hydride, alkyllithium, lithium alkoxide, lithium hydroxide or the like.
- the unreacted 2-pyrrolidone may be polymerized without removing the formed 2-pyrrolidone lithium salt.
- the 2-pyrrolidone lithium salt previously prepared by the above method may be added to the polymerization solution containing 2-pyrrolidone.
- the amount of use of the 2-pyrrolidone lithium salt can be such as 0.1 to 20 mol%, 1 to 20 mol%, 1 to 15 mol%, etc. based on the 2-pyrrolidone to be polymerized.
- 2-pyrrolidone sodium salt can be further used in the production method of the present invention.
- the 2-pyrrolidone sodium salt can be prepared by reacting 2-pyrrolidone with metallic sodium, sodium hydride, sodium amide, sodium alkoxide, sodium hydroxide and the like. In the polymerization, it can be added in the same formulation as 2-pyridone lithium salt. The rate of the polymerization reaction can be accelerated by using 2-pyrrolidone sodium salt.
- the amount of 2-pyrrolidone sodium salt used is such as 0.01 to 20 mol%, 0.1 to 20 mol%, 0.1 to 10 mol%, etc. based on the 2-pyrrolidone to be polymerized. it can.
- the polymerization reaction can be carried out in the presence of other additives.
- Other additives can include surfactants.
- surfactant known surfactants such as anionic surfactants, nonionic surfactants and cationic surfactants can be used.
- the polymerization reaction of 2-pyrrolidone is carried out while stirring with a stirring blade or the like. By vigorously stirring the reaction solution, it is preferable to polymerize in a state in which 2-pyrrolidone is suspended in an aprotic solvent incompatible with 2-pyrrolidone. That is, in the production method of the present invention, the polymerization reaction of 2-pyrrolidone is preferably suspension polymerization.
- the temperature of the polymerization reaction can be set in the range of 30 ° C. to 60 ° C., 40 ° C. to 60 ° C. or the like.
- the time of the polymerization reaction varies depending on the reaction scale and the like, but is usually 1 hour to 50 hours.
- the polyamide 4 particles can be purified by a known purification method.
- Example 1 2-pyrrolidone (57.0 g) and liquid paraffin (106.5 g) were placed in a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) in a nitrogen atmosphere, and stirred at 1200 rpm. Subsequently, n-BuLi (13. 2 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (1.74 g) was added, and the mixture was stirred for 5 minutes and polymerized at 50 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (17.21 g).
- Example 2 Add 2-pyrrolidone (57.6 g), sodium amide (0.31 g), and liquid paraffin (105.6 g) to a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) and nitrogen atmosphere, and run at 1200 rpm It stirred. Subsequently, n-BuLi (13. 11 g of a 1.6 M hexane solution) was added, and the mixture was stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (1.78 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water, and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (28.66 g).
- Example 3 In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), sodium amide (0.60 g), and liquid paraffin (104.9 g) are added and stirred at 1200 rpm did. Subsequently, n-BuLi (13. 10 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (3.50 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.02 g).
- Comparative example 2 In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), potassium t-butoxide (5.30 g), and liquid paraffin (118.0 g) are added, and 1200 rpm The mixture was stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (3.53 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration.
- the obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 (38.24 g).
- the obtained polyamide 4 was in the form of granules, with some particles aggregated.
- the volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyamide 4 particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured. The results are shown in Table 1. * 2-Pyrrolidone metal salt is formed when 2-pyrrolidone is added with a metal compound such as n-BuLi. ** The particles produced in Comparative Examples 1 and 2 could not measure the volume average particle size because the particle size was too large.
- Example 4 In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and in a nitrogen atmosphere, 2-pyrrolidone (57.7 g) and sodium amide (0.64 g) hexane (98.7 g) were charged and stirred at 1200 rpm. Subsequently, n-BuLi (19.6 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (3.6 g) was added and polymerized at 30 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.58 g).
- Example 5 2-pyrrolidone (56.7 g), sodium amide (0.62 g) liquid paraffin (89.2 g), toluene (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 1 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (3.4 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours.
- polymer After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (35.57 g).
- Example 6 2-pyrrolidone (56.8 g), sodium amide (0.65 g) liquid paraffin (89.2 g), tetrahydrofuran (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 3 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl- ⁇ -caprolactam (3.5 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours.
- polymer After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (31.70 g).
- volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of each of the polyamide 4 particles obtained in Examples 4 to 6 were measured. The results are shown in Table 2.
- CV (coefficient of variation) is defined by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
- CV (%) ((standard deviation) / (average particle size)) x 100
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The purpose of the present invention is to provide a new method for producing polyamide-4 particles having a small particle diameter. The production method for polyamide-4 particles of the present invention comprises either polymerizing 2-pyrrolidone in the presence of a polymerization initiator and the lithium salt of 2-pyrrolidone in an aprotic solvent incompatible with 2-pyrrolidone or polymerizing 2-pyrrolidone in the presence of a polymerization initiator, the lithium salt of 2-pyrrolidone, and the sodium salt of 2-pyrrolidone in an aprotic solvent incompatible with 2-pyrrolidone. The obtained polyamide-4 particles have a volume-average particle diameter of 1-100 μm and have a molecular-weight distribution (Mw/Mn) of 1.0-5.0.
Description
本発明は、ポリアミド４粒子の製造方法に関する。
本願は、２０１７年１０月３日に出願された日本国特許出願第２０１７－１９３５３４号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a method of producing polyamide 4 particles.
Priority is claimed on Japanese Patent Application No. 2017-193534, filed Oct. 3, 2017, the content of which is incorporated herein by reference.
本願は、２０１７年１０月３日に出願された日本国特許出願第２０１７－１９３５３４号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a method of producing polyamide 4 particles.
Priority is claimed on Japanese Patent Application No. 2017-193534, filed Oct. 3, 2017, the content of which is incorporated herein by reference.
ポリアミド４粒子は、化粧料、吸着剤、触媒の担持体、繊維などへの応用が期待されている。特許文献１には、重合用モノマーである２－ピロリドンおよび／または２－アゼチジノンと塩基性重合触媒とを含有する原料混合物を、密度４５０ｋｇ／ｍ３以上の二酸化炭素を含む圧縮性流体に接触させて前記原料混合物を溶融又は溶解させた後、前記重合用モノマーを開環重合させることを特徴とするポリアミド粒子の製造方法が記載されている。特許文献１の方法によれば、ｄ５０径が１０μｍ以上１０００μｍ以下であり、分散度が３．０以下であり、多孔質であるポリアミド粒子を製造することができるようである。特許文献２には、α－ピロリドンを飽和炭化水素中で重合開始剤および触媒の外に高級脂肪酸アルカリ塩を存在させて重合する方法が記載されている。特許文献２の方法によれば、直径０．０５～２．０ｍｍ程度の均一なポリマー粒を製造することができるようである。また、特許文献３には、非プロトン性溶剤中で２－ピロリドンを塩基性重合触媒および重合開始剤の炭酸ガスまたは二酸化硫黄の作用で懸濁重合する際に、２－ピロリドンに対して、化学式（１）であらわされる化合物を０．１～５重量％存在させる粉末状２－ピロリドン重合体の製造方法が記載されている。
（ＲＣＯＯ）１／２Ｍ （１）
（ここでＲは炭素数１０～３０の炭化水素基、Ｍは２価の金属） The polyamide 4 particles are expected to be applied to cosmetics, adsorbents, carriers of catalysts, fibers and the like. According to Patent Document 1, a raw material mixture containing 2-pyrrolidone and / or 2-azetidinone as polymerization monomers and a basic polymerization catalyst is brought into contact with a compressible fluid containing carbon dioxide having a density of 450 kg / m 3 or more. A method for producing polyamide particles is described, which comprises melting or dissolving the raw material mixture and then ring-opening polymerizing the polymerization monomer. According to the method of Patent Document 1, it is possible to produce polyamide particles having a d50 diameter of 10 μm to 1000 μm, a dispersion degree of 3.0 or less, and being porous. Patent Document 2 describes a method of polymerizing α-pyrrolidone in a saturated hydrocarbon in the presence of a higher fatty acid alkali salt in addition to a polymerization initiator and a catalyst. According to the method of Patent Document 2, it seems that uniform polymer particles having a diameter of about 0.05 to 2.0 mm can be produced. Patent Document 3 also describes the chemical formula for 2-pyrrolidone in the case of suspension polymerization of 2-pyrrolidone by the action of a basic polymerization catalyst and a carbon dioxide gas or sulfur dioxide of a polymerization initiator in an aprotic solvent. A process for producing a powdered 2-pyrrolidone polymer in which 0.1 to 5% by weight of the compound represented by (1) is present is described.
(RCOO) 1/2 M (1)
(Where R is a hydrocarbon group having 10 to 30 carbon atoms, and M is a divalent metal)
（ＲＣＯＯ）１／２Ｍ （１）
（ここでＲは炭素数１０～３０の炭化水素基、Ｍは２価の金属） The polyamide 4 particles are expected to be applied to cosmetics, adsorbents, carriers of catalysts, fibers and the like. According to Patent Document 1, a raw material mixture containing 2-pyrrolidone and / or 2-azetidinone as polymerization monomers and a basic polymerization catalyst is brought into contact with a compressible fluid containing carbon dioxide having a density of 450 kg / m 3 or more. A method for producing polyamide particles is described, which comprises melting or dissolving the raw material mixture and then ring-opening polymerizing the polymerization monomer. According to the method of Patent Document 1, it is possible to produce polyamide particles having a d50 diameter of 10 μm to 1000 μm, a dispersion degree of 3.0 or less, and being porous. Patent Document 2 describes a method of polymerizing α-pyrrolidone in a saturated hydrocarbon in the presence of a higher fatty acid alkali salt in addition to a polymerization initiator and a catalyst. According to the method of Patent Document 2, it seems that uniform polymer particles having a diameter of about 0.05 to 2.0 mm can be produced. Patent Document 3 also describes the chemical formula for 2-pyrrolidone in the case of suspension polymerization of 2-pyrrolidone by the action of a basic polymerization catalyst and a carbon dioxide gas or sulfur dioxide of a polymerization initiator in an aprotic solvent. A process for producing a powdered 2-pyrrolidone polymer in which 0.1 to 5% by weight of the compound represented by (1) is present is described.
(RCOO) 1/2 M (1)
(Where R is a hydrocarbon group having 10 to 30 carbon atoms, and M is a divalent metal)
特許文献１に記載された方法は、特殊な装置が必要となるため、工業的な生産には適していなかった。また、特許文献２や特許文献３に記載された方法は、生成するポリアミド４粒子の粒径が大きくなる傾向があるため、より小さな粒径を有するポリアミド４粒子の製造方法としては適していなかった。本発明は、粒径の小さなポリアミド４粒子を製造する新しい方法を提供することを目的とする。
The method described in Patent Document 1 is not suitable for industrial production because it requires special equipment. Further, the methods described in Patent Document 2 and Patent Document 3 are not suitable as a method for producing polyamide 4 particles having a smaller particle diameter because the particle diameter of the produced polyamide 4 particles tends to increase. . The present invention aims to provide a new method of producing polyamide 4 particles of small particle size.
有機溶媒中、重合開始剤および２－ピロリドンリチウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法を見出し、本発明を完成するに至った。
The inventors have found a method for producing polyamide 4 particles in which 2-pyrrolidone is polymerized in an organic solvent in the presence of a polymerization initiator and 2-pyrrolidone lithium salt, and the present invention has been completed.
即ち、本発明は、以下の発明に関する。
（１）２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤および２－ピロリドンリチウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。
（２）２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤、２－ピロリドンリチウム塩および２－ピロリドンナトリウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。
（３）２－ピロリドンと相溶しない非プロトン性溶媒が、脂肪族炭化水素系溶媒である（１）または（２）に記載のポリアミド４粒子の製造方法。
（４）ポリアミド４粒子の体積平均粒径が、１μｍ～１００μｍである（１）～（３）のいずれかに記載のポリアミド４粒子の製造方法。
（５）ポリアミド４粒子の分子量分布（Ｍｗ／Ｍｎ）が、１．０～５．０である（１）～（４）のいずれかに記載のポリアミド４粒子の製造方法。 That is, the present invention relates to the following inventions.
(1) A method for producing polyamide 4 particles, wherein 2-pyrrolidone is polymerized in the presence of a polymerization initiator and 2-pyrrolidone lithium salt in an aprotic solvent incompatible with 2-pyrrolidone.
(2) A method for producing polyamide 4 particles, wherein 2-pyrrolidone is polymerized in the presence of a polymerization initiator, 2-pyrrolidone lithium salt and 2-pyrrolidone sodium salt in an aprotic solvent incompatible with 2-pyrrolidone.
(3) The method for producing polyamide 4 particles according to (1) or (2), wherein the aprotic solvent incompatible with 2-pyrrolidone is an aliphatic hydrocarbon solvent.
(4) The method for producing polyamide 4 particles according to any one of (1) to (3), wherein the volume average particle diameter of the polyamide 4 particles is 1 μm to 100 μm.
(5) The method for producing polyamide 4 particles according to any one of (1) to (4), wherein the molecular weight distribution (Mw / Mn) of the polyamide 4 particles is 1.0 to 5.0.
（１）２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤および２－ピロリドンリチウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。
（２）２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤、２－ピロリドンリチウム塩および２－ピロリドンナトリウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。
（３）２－ピロリドンと相溶しない非プロトン性溶媒が、脂肪族炭化水素系溶媒である（１）または（２）に記載のポリアミド４粒子の製造方法。
（４）ポリアミド４粒子の体積平均粒径が、１μｍ～１００μｍである（１）～（３）のいずれかに記載のポリアミド４粒子の製造方法。
（５）ポリアミド４粒子の分子量分布（Ｍｗ／Ｍｎ）が、１．０～５．０である（１）～（４）のいずれかに記載のポリアミド４粒子の製造方法。 That is, the present invention relates to the following inventions.
(1) A method for producing polyamide 4 particles, wherein 2-pyrrolidone is polymerized in the presence of a polymerization initiator and 2-pyrrolidone lithium salt in an aprotic solvent incompatible with 2-pyrrolidone.
(2) A method for producing polyamide 4 particles, wherein 2-pyrrolidone is polymerized in the presence of a polymerization initiator, 2-pyrrolidone lithium salt and 2-pyrrolidone sodium salt in an aprotic solvent incompatible with 2-pyrrolidone.
(3) The method for producing polyamide 4 particles according to (1) or (2), wherein the aprotic solvent incompatible with 2-pyrrolidone is an aliphatic hydrocarbon solvent.
(4) The method for producing polyamide 4 particles according to any one of (1) to (3), wherein the volume average particle diameter of the polyamide 4 particles is 1 μm to 100 μm.
(5) The method for producing polyamide 4 particles according to any one of (1) to (4), wherein the molecular weight distribution (Mw / Mn) of the polyamide 4 particles is 1.0 to 5.0.
本発明の製造方法により、粒径の小さなポリアミド４粒子を製造することができる。
According to the production method of the present invention, polyamide 4 particles having a small particle size can be produced.
（ポリアミド４粒子）
ポリアミド４粒子とは、２－ピロリドンを重合させて得られるポリアミド４からなる粒子である。２－ピロリドンは市販品を用いることができる。
本発明のポリアミド４粒子の体積平均粒径は、１μｍ～１００μｍ、１μｍ～８０μｍ、１μｍ～７０μｍ、１μｍ～６０μｍ、１μｍ～５０μｍ、１μｍ～４０μｍ、または１μｍ～３０μｍである。本発明のポリアミド４粒子の体積平均粒径は、製造したポリアミド４粒子を水と混合したものを超音波分散した後に、レーザー回析／散乱式粒度分布測定装置ＬＡ－９２０（堀場製作所（株）製）により求めることができる。また、本発明のポリアミド４粒子のＣＶ（変動係数）は、体積基準の粒度分布における標準偏差および平均粒径の値を用いて下記式により算出することができる。
ＣＶ（％）＝（（標準偏差）／（平均粒径））×１００ (Polyamide 4 particles)
The polyamide 4 particles are particles made of polyamide 4 obtained by polymerizing 2-pyrrolidone. Commercially available 2-pyrrolidone can be used.
The volume average particle diameter of the polyamide 4 particles of the present invention is 1 μm to 100 μm, 1 μm to 80 μm, 1 μm to 70 μm, 1 μm to 60 μm, 1 μm to 50 μm, 1 μm to 40 μm, or 1 μm to 30 μm. The volume average particle diameter of the polyamide 4 particles of the present invention is obtained by ultrasonically dispersing a mixture of the produced polyamide 4 particles with water, and then using a laser diffraction / scattering type particle size distribution analyzer LA-920 (Horiba, Ltd.) Product). The CV (coefficient of variation) of the polyamide 4 particles of the present invention can be calculated by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
CV (%) = ((standard deviation) / (average particle size)) x 100
ポリアミド４粒子とは、２－ピロリドンを重合させて得られるポリアミド４からなる粒子である。２－ピロリドンは市販品を用いることができる。
本発明のポリアミド４粒子の体積平均粒径は、１μｍ～１００μｍ、１μｍ～８０μｍ、１μｍ～７０μｍ、１μｍ～６０μｍ、１μｍ～５０μｍ、１μｍ～４０μｍ、または１μｍ～３０μｍである。本発明のポリアミド４粒子の体積平均粒径は、製造したポリアミド４粒子を水と混合したものを超音波分散した後に、レーザー回析／散乱式粒度分布測定装置ＬＡ－９２０（堀場製作所（株）製）により求めることができる。また、本発明のポリアミド４粒子のＣＶ（変動係数）は、体積基準の粒度分布における標準偏差および平均粒径の値を用いて下記式により算出することができる。
ＣＶ（％）＝（（標準偏差）／（平均粒径））×１００ (Polyamide 4 particles)
The polyamide 4 particles are particles made of polyamide 4 obtained by polymerizing 2-pyrrolidone. Commercially available 2-pyrrolidone can be used.
The volume average particle diameter of the polyamide 4 particles of the present invention is 1 μm to 100 μm, 1 μm to 80 μm, 1 μm to 70 μm, 1 μm to 60 μm, 1 μm to 50 μm, 1 μm to 40 μm, or 1 μm to 30 μm. The volume average particle diameter of the polyamide 4 particles of the present invention is obtained by ultrasonically dispersing a mixture of the produced polyamide 4 particles with water, and then using a laser diffraction / scattering type particle size distribution analyzer LA-920 (Horiba, Ltd.) Product). The CV (coefficient of variation) of the polyamide 4 particles of the present invention can be calculated by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
CV (%) = ((standard deviation) / (average particle size)) x 100
本発明の方法で製造するポリアミド４の重量平均分子量（Ｍｗ）は、特に限定されないが、５，０００～１，０００，０００、１０，０００～１，０００，０００、１０，０００～５００，０００、１０,０００～１００,０００などを選択することができる。また、本発明の方法で製造するポリアミド４の分子量分布は、重量平均分子量／数平均分子量（Ｍｗ／Ｍｎ）の比で、１．０～６．０、１．０～４．５、１．０～４．０、１．０～３．５、１．０～３．０などを選択することができる。なお、重量平均分子量および数平均分子量はヘキサフロロイソプロパノールを溶媒とするゲルパーミエーションクロマトグラフィ（ＧＰＣ）にて測定したデータを標準ポリメチルメタクリレートの分子量に基づいて換算した値である。
The weight average molecular weight (Mw) of the polyamide 4 produced by the method of the present invention is not particularly limited, but 5,000 to 1,000,000, 10,000 to 1,000,000, 10,000 to 500,000. , 10,000 to 100,000, etc. can be selected. Further, the molecular weight distribution of the polyamide 4 produced by the method of the present invention is 1.0 to 6.0, 1.0 to 4.5, 1. in the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). 0 to 4.0, 1.0 to 3.5, 1.0 to 3.0 and the like can be selected. The weight average molecular weight and the number average molecular weight are values obtained by converting data measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent based on the molecular weight of standard polymethyl methacrylate.
（２－ピロリドンと相溶しない非プロトン性溶媒）
本発明の製造方法では、２－ピロリドンと相溶しない非プロトン性溶媒中で重合をおこなう。２－ピロリドンと相溶しない非プロトン性溶媒としては、ヘキサン、オクタン、デカン、ドデカン、ウンデカン、トリデカン、デカリン、２，２，４，６，６－ペンタメチルヘプタン、シクロヘキサン、デセン、イソパラフィン、流動パラフィン、ケロシン、石油エーテルなどの脂肪族炭化水素系溶媒を挙げることができる。これら溶媒は、１種単独でまたは２種以上を組み合わせて使用することができる。本件発明の２－ピロリドンと相溶しない非プロトン性溶媒は、２－ピロリドンと相溶する非プロトン性溶媒と、２－ピロリドンと相溶しない非プロトン性溶媒との混合溶媒であって、２－ピロリドンと相溶しない混合溶媒をも包含する。２－ピロリドンと相溶する非プロトン性溶媒としては、トルエン、シクロペンチルメチルエーテル、テトラヒドロフランなどを挙げることができる。
非プロトン性溶媒の使用量は、反応スケールなどに合わせて適宜設定することができる。通常は、２－ピロリドン１重量部に対して、非プロトン性溶媒を０．１～３０重量部、０．１～２０重量部、０．１～１０重量部、０．１～５重量部、０．５～５重量部などの範囲で設定することができる。 (Aprotic solvent incompatible with 2-pyrrolidone)
In the production method of the present invention, the polymerization is carried out in an aprotic solvent incompatible with 2-pyrrolidone. The aprotic solvent incompatible with 2-pyrrolidone is hexane, octane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, cyclohexane, decene, isoparaffin, liquid paraffin And aliphatic hydrocarbon solvents such as kerosene and petroleum ether. These solvents can be used singly or in combination of two or more. The aprotic solvent incompatible with 2-pyrrolidone of the present invention is a mixed solvent of an aprotic solvent compatible with 2-pyrrolidone and an aprotic solvent incompatible with 2-pyrrolidone, wherein It also includes mixed solvents incompatible with pyrrolidone. Examples of the aprotic solvent compatible with 2-pyrrolidone include toluene, cyclopentyl methyl ether, tetrahydrofuran and the like.
The amount of the aprotic solvent used can be appropriately set according to the reaction scale and the like. Usually, 0.1 to 30 parts by weight, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight, 0.1 to 5 parts by weight of an aprotic solvent to 1 part by weight of 2-pyrrolidone, It can be set in the range of 0.5 to 5 parts by weight or the like.
本発明の製造方法では、２－ピロリドンと相溶しない非プロトン性溶媒中で重合をおこなう。２－ピロリドンと相溶しない非プロトン性溶媒としては、ヘキサン、オクタン、デカン、ドデカン、ウンデカン、トリデカン、デカリン、２，２，４，６，６－ペンタメチルヘプタン、シクロヘキサン、デセン、イソパラフィン、流動パラフィン、ケロシン、石油エーテルなどの脂肪族炭化水素系溶媒を挙げることができる。これら溶媒は、１種単独でまたは２種以上を組み合わせて使用することができる。本件発明の２－ピロリドンと相溶しない非プロトン性溶媒は、２－ピロリドンと相溶する非プロトン性溶媒と、２－ピロリドンと相溶しない非プロトン性溶媒との混合溶媒であって、２－ピロリドンと相溶しない混合溶媒をも包含する。２－ピロリドンと相溶する非プロトン性溶媒としては、トルエン、シクロペンチルメチルエーテル、テトラヒドロフランなどを挙げることができる。
非プロトン性溶媒の使用量は、反応スケールなどに合わせて適宜設定することができる。通常は、２－ピロリドン１重量部に対して、非プロトン性溶媒を０．１～３０重量部、０．１～２０重量部、０．１～１０重量部、０．１～５重量部、０．５～５重量部などの範囲で設定することができる。 (Aprotic solvent incompatible with 2-pyrrolidone)
In the production method of the present invention, the polymerization is carried out in an aprotic solvent incompatible with 2-pyrrolidone. The aprotic solvent incompatible with 2-pyrrolidone is hexane, octane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, cyclohexane, decene, isoparaffin, liquid paraffin And aliphatic hydrocarbon solvents such as kerosene and petroleum ether. These solvents can be used singly or in combination of two or more. The aprotic solvent incompatible with 2-pyrrolidone of the present invention is a mixed solvent of an aprotic solvent compatible with 2-pyrrolidone and an aprotic solvent incompatible with 2-pyrrolidone, wherein It also includes mixed solvents incompatible with pyrrolidone. Examples of the aprotic solvent compatible with 2-pyrrolidone include toluene, cyclopentyl methyl ether, tetrahydrofuran and the like.
The amount of the aprotic solvent used can be appropriately set according to the reaction scale and the like. Usually, 0.1 to 30 parts by weight, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight, 0.1 to 5 parts by weight of an aprotic solvent to 1 part by weight of 2-pyrrolidone, It can be set in the range of 0.5 to 5 parts by weight or the like.
（重合開始剤）
重合開始剤としては、２－ピロリドンを重合する際に用いられる公知の重合開始剤を用いることができる。重合開始剤としては、具体的に、炭酸ガス（ＣＯ２）；二酸化硫黄（ＳＯ２）；Ｎ－アセチルピロリドン、Ｎ－アセチルε－カプロラクタム等のラクタム類のアシル化物；塩化アセチル、塩化ステアロイル、ベンゼン－１，３，５－トリカルボニルトリクロリドなどのカルボン酸ハロゲン化物；無水酢酸、無水フタル酸などのカルボン酸無水物；カルボン酸メチルエステルなどのカルボン酸エステル；２，４－ジイソシアン酸トリレンなどのイソシアネート化合物や、これらの重合開始剤と重合触媒との反応物などを挙げることができる。これらの重合開始剤は、１種単独でまたは２種以上を組み合わせて使用することができる。
重合開始剤の使用量は、重合する２－ピロリドンに対して、０．０１～２０モル％、０．１～１０モル％などの使用量とすることができる。 (Polymerization initiator)
As the polymerization initiator, known polymerization initiators used when polymerizing 2-pyrrolidone can be used. Specific examples of the polymerization initiator include carbon dioxide gas (CO 2 ); sulfur dioxide (SO 2 ); N-acetyl pyrrolidone, N-acetyl ε-caprolactam, and other acylated compounds of lactams; acetyl chloride, stearoyl chloride, benzene -Carboxylic acid halides such as -1,3,5-tricarbonyl trichloride; Carboxylic acid anhydrides such as acetic anhydride and phthalic acid anhydride; Carboxylic acid esters such as carboxylic acid methyl ester; and Tolylene 2,4-diisocyanate An isocyanate compound, the reaction product of these polymerization initiators and a polymerization catalyst, etc. can be mentioned. These polymerization initiators can be used singly or in combination of two or more.
The amount of the polymerization initiator used can be such as from 0.01 to 20 mol%, such as 0.1 to 10 mol%, based on the 2-pyrrolidone to be polymerized.
重合開始剤としては、２－ピロリドンを重合する際に用いられる公知の重合開始剤を用いることができる。重合開始剤としては、具体的に、炭酸ガス（ＣＯ２）；二酸化硫黄（ＳＯ２）；Ｎ－アセチルピロリドン、Ｎ－アセチルε－カプロラクタム等のラクタム類のアシル化物；塩化アセチル、塩化ステアロイル、ベンゼン－１，３，５－トリカルボニルトリクロリドなどのカルボン酸ハロゲン化物；無水酢酸、無水フタル酸などのカルボン酸無水物；カルボン酸メチルエステルなどのカルボン酸エステル；２，４－ジイソシアン酸トリレンなどのイソシアネート化合物や、これらの重合開始剤と重合触媒との反応物などを挙げることができる。これらの重合開始剤は、１種単独でまたは２種以上を組み合わせて使用することができる。
重合開始剤の使用量は、重合する２－ピロリドンに対して、０．０１～２０モル％、０．１～１０モル％などの使用量とすることができる。 (Polymerization initiator)
As the polymerization initiator, known polymerization initiators used when polymerizing 2-pyrrolidone can be used. Specific examples of the polymerization initiator include carbon dioxide gas (CO 2 ); sulfur dioxide (SO 2 ); N-acetyl pyrrolidone, N-acetyl ε-caprolactam, and other acylated compounds of lactams; acetyl chloride, stearoyl chloride, benzene -Carboxylic acid halides such as -1,3,5-tricarbonyl trichloride; Carboxylic acid anhydrides such as acetic anhydride and phthalic acid anhydride; Carboxylic acid esters such as carboxylic acid methyl ester; and Tolylene 2,4-diisocyanate An isocyanate compound, the reaction product of these polymerization initiators and a polymerization catalyst, etc. can be mentioned. These polymerization initiators can be used singly or in combination of two or more.
The amount of the polymerization initiator used can be such as from 0.01 to 20 mol%, such as 0.1 to 10 mol%, based on the 2-pyrrolidone to be polymerized.
（２－ピロリドンリチウム塩）
本発明の製造方法では、２－ピロリドンリチウム塩の存在下、２－ピロリドンの重合をおこなう。詳細は明らかではないが、２－ピロリドンリチウム塩は固体として析出し、これがモノマー／溶媒界面に吸着することで懸濁状態を安定化していると思われる。２－ピロリドンリチウム塩は、２－ピロリドンと金属リチウム、水素化リチウム、アルキルリチウム、リチウムアルコキシド、水酸化リチウム等を反応させることで調製することができる。重合に際しては、重合用の２－ピロリドンにリチウム化合物を添加して反応させた後、生成した２－ピロリドンリチウム塩を取り出すことなく、未反応の２－ピロリドンを重合するようにしてもよいし、あらかじめ上記方法により調製して得た２－ピロリドンリチウム塩を２－ピロリドンを含有する重合溶液に添加してもよい。
２－ピロリドンリチウム塩の使用量は、重合する２－ピロリドンに対して、０．１～２０モル％、１～２０モル％、１～１５モル％などの使用量とすることができる。
本発明の製造方法では、２－ピロリドンリチウム塩に加えて、さらに、２－ピロリドンナトリウム塩を使用することができる。２－ピロリドンナトリウム塩は、２－ピロリドンと金属ナトリウム、水素化ナトリウム、ナトリウムアミド、ナトリウムアルコキシド、水酸化ナトリウム等を反応させることで調製することができる。重合に際しては、２－ピリドンリチウム塩と同様の処方で添加することができる。
２－ピロリドンナトリウム塩を使用することにより、重合反応の速度を促進することができる。２－ピロリドンナトリウム塩の使用量は、重合する２－ピロリドンに対して、０．０１～２０モル％、０．１～２０モル％、０．１～１０モル％などの使用量とすることができる。 (2-pyrrolidone lithium salt)
In the production method of the present invention, polymerization of 2-pyrrolidone is carried out in the presence of lithium 2-pyrrolidone. Although the details are not clear, it is believed that 2-pyrrolidone lithium salt precipitates as a solid and this is adsorbed to the monomer / solvent interface to stabilize the suspended state. The 2-pyrrolidone lithium salt can be prepared by reacting 2-pyrrolidone with metal lithium, lithium hydride, alkyllithium, lithium alkoxide, lithium hydroxide or the like. At the time of polymerization, after reacting a 2-pyrrolidone for polymerization by adding a lithium compound and reacting, the unreacted 2-pyrrolidone may be polymerized without removing the formed 2-pyrrolidone lithium salt. The 2-pyrrolidone lithium salt previously prepared by the above method may be added to the polymerization solution containing 2-pyrrolidone.
The amount of use of the 2-pyrrolidone lithium salt can be such as 0.1 to 20 mol%, 1 to 20 mol%, 1 to 15 mol%, etc. based on the 2-pyrrolidone to be polymerized.
In addition to 2-pyrrolidone lithium salt, 2-pyrrolidone sodium salt can be further used in the production method of the present invention. The 2-pyrrolidone sodium salt can be prepared by reacting 2-pyrrolidone with metallic sodium, sodium hydride, sodium amide, sodium alkoxide, sodium hydroxide and the like. In the polymerization, it can be added in the same formulation as 2-pyridone lithium salt.
The rate of the polymerization reaction can be accelerated by using 2-pyrrolidone sodium salt. The amount of 2-pyrrolidone sodium salt used is such as 0.01 to 20 mol%, 0.1 to 20 mol%, 0.1 to 10 mol%, etc. based on the 2-pyrrolidone to be polymerized. it can.
本発明の製造方法では、２－ピロリドンリチウム塩の存在下、２－ピロリドンの重合をおこなう。詳細は明らかではないが、２－ピロリドンリチウム塩は固体として析出し、これがモノマー／溶媒界面に吸着することで懸濁状態を安定化していると思われる。２－ピロリドンリチウム塩は、２－ピロリドンと金属リチウム、水素化リチウム、アルキルリチウム、リチウムアルコキシド、水酸化リチウム等を反応させることで調製することができる。重合に際しては、重合用の２－ピロリドンにリチウム化合物を添加して反応させた後、生成した２－ピロリドンリチウム塩を取り出すことなく、未反応の２－ピロリドンを重合するようにしてもよいし、あらかじめ上記方法により調製して得た２－ピロリドンリチウム塩を２－ピロリドンを含有する重合溶液に添加してもよい。
２－ピロリドンリチウム塩の使用量は、重合する２－ピロリドンに対して、０．１～２０モル％、１～２０モル％、１～１５モル％などの使用量とすることができる。
本発明の製造方法では、２－ピロリドンリチウム塩に加えて、さらに、２－ピロリドンナトリウム塩を使用することができる。２－ピロリドンナトリウム塩は、２－ピロリドンと金属ナトリウム、水素化ナトリウム、ナトリウムアミド、ナトリウムアルコキシド、水酸化ナトリウム等を反応させることで調製することができる。重合に際しては、２－ピリドンリチウム塩と同様の処方で添加することができる。
２－ピロリドンナトリウム塩を使用することにより、重合反応の速度を促進することができる。２－ピロリドンナトリウム塩の使用量は、重合する２－ピロリドンに対して、０．０１～２０モル％、０．１～２０モル％、０．１～１０モル％などの使用量とすることができる。 (2-pyrrolidone lithium salt)
In the production method of the present invention, polymerization of 2-pyrrolidone is carried out in the presence of lithium 2-pyrrolidone. Although the details are not clear, it is believed that 2-pyrrolidone lithium salt precipitates as a solid and this is adsorbed to the monomer / solvent interface to stabilize the suspended state. The 2-pyrrolidone lithium salt can be prepared by reacting 2-pyrrolidone with metal lithium, lithium hydride, alkyllithium, lithium alkoxide, lithium hydroxide or the like. At the time of polymerization, after reacting a 2-pyrrolidone for polymerization by adding a lithium compound and reacting, the unreacted 2-pyrrolidone may be polymerized without removing the formed 2-pyrrolidone lithium salt. The 2-pyrrolidone lithium salt previously prepared by the above method may be added to the polymerization solution containing 2-pyrrolidone.
The amount of use of the 2-pyrrolidone lithium salt can be such as 0.1 to 20 mol%, 1 to 20 mol%, 1 to 15 mol%, etc. based on the 2-pyrrolidone to be polymerized.
In addition to 2-pyrrolidone lithium salt, 2-pyrrolidone sodium salt can be further used in the production method of the present invention. The 2-pyrrolidone sodium salt can be prepared by reacting 2-pyrrolidone with metallic sodium, sodium hydride, sodium amide, sodium alkoxide, sodium hydroxide and the like. In the polymerization, it can be added in the same formulation as 2-pyridone lithium salt.
The rate of the polymerization reaction can be accelerated by using 2-pyrrolidone sodium salt. The amount of 2-pyrrolidone sodium salt used is such as 0.01 to 20 mol%, 0.1 to 20 mol%, 0.1 to 10 mol%, etc. based on the 2-pyrrolidone to be polymerized. it can.
（他の添加剤）
本発明の製造方法においては、他の添加剤の存在下に重合反応をおこなうことができる。他の添加剤としては、界面活性剤を挙げることができる。界面活性剤としてはアニオン性界面活性剤、非イオン性界面活性剤やカチオン性界面活性剤などの公知の界面活性剤を用いることができる。 (Other additives)
In the production method of the present invention, the polymerization reaction can be carried out in the presence of other additives. Other additives can include surfactants. As the surfactant, known surfactants such as anionic surfactants, nonionic surfactants and cationic surfactants can be used.
本発明の製造方法においては、他の添加剤の存在下に重合反応をおこなうことができる。他の添加剤としては、界面活性剤を挙げることができる。界面活性剤としてはアニオン性界面活性剤、非イオン性界面活性剤やカチオン性界面活性剤などの公知の界面活性剤を用いることができる。 (Other additives)
In the production method of the present invention, the polymerization reaction can be carried out in the presence of other additives. Other additives can include surfactants. As the surfactant, known surfactants such as anionic surfactants, nonionic surfactants and cationic surfactants can be used.
（重合条件など）
本発明の製造方法において、２－ピロリドンの重合反応は、撹拌翼などで撹拌しながらおこなう。反応溶液を激しく撹拌することにより、２－ピロリドンと相溶しない非プロトン性溶媒中に２－ピロリドンが懸濁した状態で重合するのが好ましい。すなわち、本発明の製造方法において、２－ピロリドンの重合反応は、懸濁重合であるのが好ましい。重合反応の温度は、３０℃～６０℃、４０℃～６０℃などの範囲で設定することができる。重合反応の時間は、反応スケールなどにより変わるが、通常は、１時間～５０時間である。重合反応終了後は、公知の精製方法によりポリアミド４粒子を精製することができる。 (Such as polymerization conditions)
In the production method of the present invention, the polymerization reaction of 2-pyrrolidone is carried out while stirring with a stirring blade or the like. By vigorously stirring the reaction solution, it is preferable to polymerize in a state in which 2-pyrrolidone is suspended in an aprotic solvent incompatible with 2-pyrrolidone. That is, in the production method of the present invention, the polymerization reaction of 2-pyrrolidone is preferably suspension polymerization. The temperature of the polymerization reaction can be set in the range of 30 ° C. to 60 ° C., 40 ° C. to 60 ° C. or the like. The time of the polymerization reaction varies depending on the reaction scale and the like, but is usually 1 hour to 50 hours. After completion of the polymerization reaction, the polyamide 4 particles can be purified by a known purification method.
本発明の製造方法において、２－ピロリドンの重合反応は、撹拌翼などで撹拌しながらおこなう。反応溶液を激しく撹拌することにより、２－ピロリドンと相溶しない非プロトン性溶媒中に２－ピロリドンが懸濁した状態で重合するのが好ましい。すなわち、本発明の製造方法において、２－ピロリドンの重合反応は、懸濁重合であるのが好ましい。重合反応の温度は、３０℃～６０℃、４０℃～６０℃などの範囲で設定することができる。重合反応の時間は、反応スケールなどにより変わるが、通常は、１時間～５０時間である。重合反応終了後は、公知の精製方法によりポリアミド４粒子を精製することができる。 (Such as polymerization conditions)
In the production method of the present invention, the polymerization reaction of 2-pyrrolidone is carried out while stirring with a stirring blade or the like. By vigorously stirring the reaction solution, it is preferable to polymerize in a state in which 2-pyrrolidone is suspended in an aprotic solvent incompatible with 2-pyrrolidone. That is, in the production method of the present invention, the polymerization reaction of 2-pyrrolidone is preferably suspension polymerization. The temperature of the polymerization reaction can be set in the range of 30 ° C. to 60 ° C., 40 ° C. to 60 ° C. or the like. The time of the polymerization reaction varies depending on the reaction scale and the like, but is usually 1 hour to 50 hours. After completion of the polymerization reaction, the polyamide 4 particles can be purified by a known purification method.
以下実施例を用いて本発明をさらに詳細に説明するが、本発明は実施例の範囲に限定されるものではない。
The present invention will be described in more detail using the following examples, but the present invention is not limited to the scope of the examples.
実施例１
エッジドタービン翼（直径４ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．０ｇ）、流動パラフィン（１０６．５ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．２ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（１．７４ｇ）を加え５分間撹拌後、５０℃にて７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（１７．２１ｇ）を得た。 Example 1
2-pyrrolidone (57.0 g) and liquid paraffin (106.5 g) were placed in a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) in a nitrogen atmosphere, and stirred at 1200 rpm. Subsequently, n-BuLi (13. 2 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (1.74 g) was added, and the mixture was stirred for 5 minutes and polymerized at 50 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (17.21 g).
エッジドタービン翼（直径４ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．０ｇ）、流動パラフィン（１０６．５ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．２ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（１．７４ｇ）を加え５分間撹拌後、５０℃にて７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（１７．２１ｇ）を得た。 Example 1
2-pyrrolidone (57.0 g) and liquid paraffin (106.5 g) were placed in a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) in a nitrogen atmosphere, and stirred at 1200 rpm. Subsequently, n-BuLi (13. 2 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (1.74 g) was added, and the mixture was stirred for 5 minutes and polymerized at 50 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (17.21 g).
実施例２
エッジドタービン翼（直径４ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．６ｇ）、ナトリウムアミド（０．３１ｇ）、および流動パラフィン（１０５．６ｇ）を加え、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１１ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（１．７８ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（２８．６６ｇ）を得た。 Example 2
Add 2-pyrrolidone (57.6 g), sodium amide (0.31 g), and liquid paraffin (105.6 g) to a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) and nitrogen atmosphere, and run at 1200 rpm It stirred. Subsequently, n-BuLi (13. 11 g of a 1.6 M hexane solution) was added, and the mixture was stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (1.78 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water, and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (28.66 g).
エッジドタービン翼（直径４ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．６ｇ）、ナトリウムアミド（０．３１ｇ）、および流動パラフィン（１０５．６ｇ）を加え、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１１ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（１．７８ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（２８．６６ｇ）を得た。 Example 2
Add 2-pyrrolidone (57.6 g), sodium amide (0.31 g), and liquid paraffin (105.6 g) to a 300 ml separable flask equipped with an edged turbine blade (diameter 4 cm) and nitrogen atmosphere, and run at 1200 rpm It stirred. Subsequently, n-BuLi (13. 11 g of a 1.6 M hexane solution) was added, and the mixture was stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (1.78 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water, and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (28.66 g).
実施例３
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．９ｇ）、ナトリウムアミド（０．６０ｇ）、および流動パラフィン（１０４．９ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１０ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５０ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３２．０２ｇ）を得た。 Example 3
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), sodium amide (0.60 g), and liquid paraffin (104.9 g) are added and stirred at 1200 rpm did. Subsequently, n-BuLi (13. 10 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.50 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.02 g).
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．９ｇ）、ナトリウムアミド（０．６０ｇ）、および流動パラフィン（１０４．９ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１０ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５０ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３２．０２ｇ）を得た。 Example 3
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), sodium amide (0.60 g), and liquid paraffin (104.9 g) are added and stirred at 1200 rpm did. Subsequently, n-BuLi (13. 10 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.50 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.02 g).
比較例１
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．２ｇ）、ナトリウムアミド（１．７７ｇ）流動パラフィン（１１５．９ｇ）を入れ、１２００ｒｐｍで３０℃、１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．４０ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４（４１．１６ｇ）を得た。得られたポリアミド４は、一部の粒子が凝集し、顆粒状であった。 Comparative Example 1
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (57.2 g) and sodium amide (1.77 g) liquid paraffin (115.9 g) are placed, and 30 ° C at 1200 rpm. Stir for 15 minutes. N-acetyl-ε-caprolactam (3.40 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 (41.16 g). The obtained polyamide 4 was in the form of granules, with some particles aggregated.
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．２ｇ）、ナトリウムアミド（１．７７ｇ）流動パラフィン（１１５．９ｇ）を入れ、１２００ｒｐｍで３０℃、１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．４０ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４（４１．１６ｇ）を得た。得られたポリアミド４は、一部の粒子が凝集し、顆粒状であった。 Comparative Example 1
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (57.2 g) and sodium amide (1.77 g) liquid paraffin (115.9 g) are placed, and 30 ° C at 1200 rpm. Stir for 15 minutes. N-acetyl-ε-caprolactam (3.40 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 (41.16 g). The obtained polyamide 4 was in the form of granules, with some particles aggregated.
比較例２
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．９ｇ）、ｔ－ブトキシカリウム（５．３０ｇ）、および流動パラフィン（１１８．０ｇ）を加え、１２００ｒｐｍ、３０℃にて、１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５３ｇ）を加え５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４（３８．２４ｇ）を得た。得られたポリアミド４は、一部の粒子が凝集し、顆粒状であった。 Comparative example 2
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), potassium t-butoxide (5.30 g), and liquid paraffin (118.0 g) are added, and 1200 rpm The mixture was stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.53 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 (38.24 g). The obtained polyamide 4 was in the form of granules, with some particles aggregated.
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．９ｇ）、ｔ－ブトキシカリウム（５．３０ｇ）、および流動パラフィン（１１８．０ｇ）を加え、１２００ｒｐｍ、３０℃にて、１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５３ｇ）を加え５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４（３８．２４ｇ）を得た。得られたポリアミド４は、一部の粒子が凝集し、顆粒状であった。 Comparative example 2
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere, 2-pyrrolidone (56.9 g), potassium t-butoxide (5.30 g), and liquid paraffin (118.0 g) are added, and 1200 rpm The mixture was stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.53 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 (38.24 g). The obtained polyamide 4 was in the form of granules, with some particles aggregated.
実施例１～３、比較例１，２で得られたポリアミド４粒子それぞれについて、体積平均粒径、ＣＶ（変動係数）、重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表１に示す。
＊ ２－ピロリドン金属塩は、２－ピロリドンにｎ－ＢｕＬｉなどの金属化合物を添加したときに生成する。
＊＊ 比較例１，２で生成した粒子は、粒径が大きすぎるため体積平均粒径を測定することができなかった。 The volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyamide 4 particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured. The results are shown in Table 1.
* 2-Pyrrolidone metal salt is formed when 2-pyrrolidone is added with a metal compound such as n-BuLi.
** The particles produced in Comparative Examples 1 and 2 could not measure the volume average particle size because the particle size was too large.
＊ ２－ピロリドン金属塩は、２－ピロリドンにｎ－ＢｕＬｉなどの金属化合物を添加したときに生成する。
＊＊ 比較例１，２で生成した粒子は、粒径が大きすぎるため体積平均粒径を測定することができなかった。 The volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyamide 4 particles obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were measured. The results are shown in Table 1.
* 2-Pyrrolidone metal salt is formed when 2-pyrrolidone is added with a metal compound such as n-BuLi.
** The particles produced in Comparative Examples 1 and 2 could not measure the volume average particle size because the particle size was too large.
実施例４
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．7ｇ）、ナトリウムアミド（０．６４ｇ）ヘキサン（９８．７ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １９．６ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．６ｇ）を加え３０℃にて７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３２．５８ｇ）を得た。 Example 4
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and in a nitrogen atmosphere, 2-pyrrolidone (57.7 g) and sodium amide (0.64 g) hexane (98.7 g) were charged and stirred at 1200 rpm. Subsequently, n-BuLi (19.6 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.6 g) was added and polymerized at 30 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.58 g).
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５７．7ｇ）、ナトリウムアミド（０．６４ｇ）ヘキサン（９８．７ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １９．６ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．６ｇ）を加え３０℃にて７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３２．５８ｇ）を得た。 Example 4
In a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and in a nitrogen atmosphere, 2-pyrrolidone (57.7 g) and sodium amide (0.64 g) hexane (98.7 g) were charged and stirred at 1200 rpm. Subsequently, n-BuLi (19.6 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.6 g) was added and polymerized at 30 ° C. for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and then dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (32.58 g).
実施例５
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．７ｇ）、ナトリウムアミド（０．６２ｇ）流動パラフィン（８９．２ｇ）、トルエン（１５．８ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．４ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３５．５７ｇ）を得た。 Example 5
2-pyrrolidone (56.7 g), sodium amide (0.62 g) liquid paraffin (89.2 g), toluene (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 1 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.4 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (35.57 g).
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．７ｇ）、ナトリウムアミド（０．６２ｇ）流動パラフィン（８９．２ｇ）、トルエン（１５．８ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．１ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．４ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３５．５７ｇ）を得た。 Example 5
2-pyrrolidone (56.7 g), sodium amide (0.62 g) liquid paraffin (89.2 g), toluene (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 1 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.4 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (35.57 g).
実施例６
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．８ｇ）、ナトリウムアミド（０．６５ｇ）流動パラフィン（８９．２ｇ）、テトラヒドロフラン（１５．８ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．３ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３１．７０ｇ）を得た。 Example 6
2-pyrrolidone (56.8 g), sodium amide (0.65 g) liquid paraffin (89.2 g), tetrahydrofuran (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 3 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.5 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (31.70 g).
ディスクタービン翼（直径５ｃｍ）を備え、窒素雰囲気とした３００ｍｌセパラブルフラスコに２－ピロリドン（５６．８ｇ）、ナトリウムアミド（０．６５ｇ）流動パラフィン（８９．２ｇ）、テトラヒドロフラン（１５．８ｇ）を入れ、１２００ｒｐｍで撹拌した。続いてｎ－ＢｕＬｉ（１．６Ｍヘキサン溶液 １３．３ｇ）を加え、３０℃で１５分間撹拌した。Ｎ－アセチル－ε－カプロラクタム（３．５ｇ）を加え、５分間撹拌した。５０℃に加温し、７時間重合させた。水及び酢酸を加えてクエンチ後、吸引濾過によりポリマーを単離した。得られたポリマーを水及びテトラヒドロフランで洗浄した後、８０℃にて減圧乾燥することでポリアミド４粒子（３１．７０ｇ）を得た。 Example 6
2-pyrrolidone (56.8 g), sodium amide (0.65 g) liquid paraffin (89.2 g), tetrahydrofuran (15.8 g) in a 300 ml separable flask equipped with a disk turbine blade (diameter 5 cm) and nitrogen atmosphere Put in and stirred at 1200 rpm. Subsequently, n-BuLi (13. 3 g of a 1.6 M hexane solution) was added and stirred at 30 ° C. for 15 minutes. N-acetyl-ε-caprolactam (3.5 g) was added and stirred for 5 minutes. The mixture was heated to 50 ° C. and polymerized for 7 hours. After quenching by addition of water and acetic acid, the polymer was isolated by suction filtration. The obtained polymer was washed with water and tetrahydrofuran, and dried under reduced pressure at 80 ° C. to obtain polyamide 4 particles (31.70 g).
実施例４～６で得られたポリアミド４粒子それぞれについて、体積平均粒径、ＣＶ（変動係数）、重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）を測定した。結果を表２に示す。
＜体積平均粒径、ＣＶ（変動係数）の測定＞
レーザー回析／散乱式粒度分布測定装置ＬＡ－９２０（堀場製作所（株）製）により求めた。得られたポリアミド４粒子を水と混合したものを超音波分散した後に測定した。
ＣＶ（変動係数）は、体積基準の粒度分布における標準偏差および平均粒径の値を用いて下記式により定義される。
ＣＶ（％）＝（（標準偏差）／（平均粒径））×１００ The volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of each of the polyamide 4 particles obtained in Examples 4 to 6 were measured. The results are shown in Table 2.
<Measurement of volume average particle diameter, CV (coefficient of variation)>
It was determined by a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.). A mixture of the obtained polyamide 4 particles and water was measured after ultrasonic dispersion.
CV (coefficient of variation) is defined by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
CV (%) = ((standard deviation) / (average particle size)) x 100
＜体積平均粒径、ＣＶ（変動係数）の測定＞
レーザー回析／散乱式粒度分布測定装置ＬＡ－９２０（堀場製作所（株）製）により求めた。得られたポリアミド４粒子を水と混合したものを超音波分散した後に測定した。
ＣＶ（変動係数）は、体積基準の粒度分布における標準偏差および平均粒径の値を用いて下記式により定義される。
ＣＶ（％）＝（（標準偏差）／（平均粒径））×１００ The volume average particle diameter, CV (coefficient of variation), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of each of the polyamide 4 particles obtained in Examples 4 to 6 were measured. The results are shown in Table 2.
<Measurement of volume average particle diameter, CV (coefficient of variation)>
It was determined by a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.). A mixture of the obtained polyamide 4 particles and water was measured after ultrasonic dispersion.
CV (coefficient of variation) is defined by the following equation using the value of the standard deviation and the average particle diameter in the volume-based particle size distribution.
CV (%) = ((standard deviation) / (average particle size)) x 100
＜重量平均分子量、分子量分布の測定＞
トリフルオロ酢酸ナトリウム１０ｍＭヘキサフルオロイソプロパノール溶液を溶媒とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定したデータを標準ポリメタクリル酸メチルの分子量にて換算することにより算出した。
分子量分布は、下記式により定義される。
分子量分布 ＝ 重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ） <Measurement of weight average molecular weight, molecular weight distribution>
The data measured by gel permeation chromatography (GPC) using a solution of sodium trifluoroacetate 10 mM in hexafluoroisopropanol as a solvent was calculated by converting the molecular weight of standard poly (methyl methacrylate).
The molecular weight distribution is defined by the following equation.
Molecular weight distribution = weight average molecular weight (Mw) / number average molecular weight (Mn)
トリフルオロ酢酸ナトリウム１０ｍＭヘキサフルオロイソプロパノール溶液を溶媒とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定したデータを標準ポリメタクリル酸メチルの分子量にて換算することにより算出した。
分子量分布は、下記式により定義される。
分子量分布 ＝ 重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ） <Measurement of weight average molecular weight, molecular weight distribution>
The data measured by gel permeation chromatography (GPC) using a solution of sodium trifluoroacetate 10 mM in hexafluoroisopropanol as a solvent was calculated by converting the molecular weight of standard poly (methyl methacrylate).
The molecular weight distribution is defined by the following equation.
Molecular weight distribution = weight average molecular weight (Mw) / number average molecular weight (Mn)
Claims (5)
- ２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤および２－ピロリドンリチウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。 A method for producing polyamide 4 particles, which polymerizes 2-pyrrolidone in the presence of a polymerization initiator and 2-pyrrolidone lithium salt in an aprotic solvent incompatible with 2-pyrrolidone.
- ２－ピロリドンと相溶しない非プロトン性溶媒中、重合開始剤、２－ピロリドンリチウム塩および２－ピロリドンナトリウム塩の存在下、２－ピロリドンを重合するポリアミド４粒子の製造方法。 A method for producing polyamide 4 particles comprising polymerizing 2-pyrrolidone in the presence of a polymerization initiator, 2-pyrrolidone lithium salt and 2-pyrrolidone sodium salt in an aprotic solvent incompatible with 2-pyrrolidone.
- ２－ピロリドンと相溶しない非プロトン性溶媒が、脂肪族炭化水素系溶媒である請求項１または２に記載のポリアミド４粒子の製造方法。 The method for producing polyamide 4 particles according to claim 1 or 2, wherein the aprotic solvent incompatible with 2-pyrrolidone is an aliphatic hydrocarbon solvent.
- ポリアミド４粒子の体積平均粒径が、１μｍ～１００μｍである請求項１～３いずれか１項に記載のポリアミド４粒子の製造方法。 The method for producing polyamide 4 particles according to any one of claims 1 to 3, wherein the volume average particle diameter of the polyamide 4 particles is 1 μm to 100 μm.
- ポリアミド４粒子の分子量分布（Ｍｗ／Ｍｎ）が、１．０～５．０である請求項１～４いずれか１項に記載のポリアミド４粒子の製造方法。 The method for producing polyamide 4 particles according to any one of claims 1 to 4, wherein the molecular weight distribution (Mw / Mn) of the polyamide 4 particles is 1.0 to 5.0.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020207005910A KR102292169B1 (en) | 2017-10-03 | 2018-09-27 | Method for producing polyamide 4 particles |
| EP18864184.9A EP3693405A4 (en) | 2017-10-03 | 2018-09-27 | Production method for polyamide-4 particles |
| CN201880063591.3A CN111164130A (en) | 2017-10-03 | 2018-09-27 | Process for producing polyamide-4 particles |
| JP2019546670A JP6851496B2 (en) | 2017-10-03 | 2018-09-27 | Method for producing 4 polyamide particles |
| US16/651,075 US20200262976A1 (en) | 2017-10-03 | 2018-09-27 | Production method for polyamide-4 particles |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-193534 | 2017-10-03 | ||
| JP2017193534 | 2017-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019069799A1 true WO2019069799A1 (en) | 2019-04-11 |
Family
ID=65995044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2018/036109 WO2019069799A1 (en) | 2017-10-03 | 2018-09-27 | Production method for polyamide-4 particles |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20200262976A1 (en) |
| EP (1) | EP3693405A4 (en) |
| JP (1) | JP6851496B2 (en) |
| KR (1) | KR102292169B1 (en) |
| CN (1) | CN111164130A (en) |
| TW (1) | TWI705985B (en) |
| WO (1) | WO2019069799A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021095749A1 (en) * | 2019-11-11 | 2021-05-20 | 株式会社クレハ | Polyamide particles and method for manufacturing the same |
| WO2022113993A1 (en) | 2020-11-30 | 2022-06-02 | 東レ株式会社 | Fine polyamide particles and production method therefor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS376746B1 (en) | 1960-04-05 | 1962-07-02 | ||
| JPH0472329A (en) * | 1990-07-12 | 1992-03-06 | Shinto Paint Co Ltd | Production of polyamide resin powder |
| JPH0539355A (en) | 1991-08-06 | 1993-02-19 | Ube Ind Ltd | Production of powdered 2-pyrrolidone polymer |
| JPH05295108A (en) * | 1992-04-14 | 1993-11-09 | Ube Ind Ltd | Production of high-purity 2-pyrrolidone polymer |
| JPH06322109A (en) * | 1993-05-07 | 1994-11-22 | Kuraray Co Ltd | Synthesis of polyamide |
| JPH07316288A (en) * | 1994-05-30 | 1995-12-05 | Unitika Ltd | Method of polymerizing epsilon-caprolactam |
| JP2009155608A (en) * | 2007-12-28 | 2009-07-16 | National Institute Of Advanced Industrial & Technology | Polyamide 4 copolymer introducing branch structure, and its producing method |
| JP2016186068A (en) | 2015-03-19 | 2016-10-27 | 株式会社リコー | Polyamide particle and production method thereof |
| JP2017193534A (en) | 2016-03-31 | 2017-10-26 | 株式会社松風 | Lithium silicate glass composition free of al2o3 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL250641A (en) * | 1959-04-20 | |||
| US4017465A (en) * | 1975-01-23 | 1977-04-12 | Chevron Research Company | Process for polymerization of 2-pyrrolidone |
| US4013626A (en) * | 1975-03-17 | 1977-03-22 | Chevron Research Company | Process for preparing polypyrrolidone wherein polypyrrolidone is washed with 2-pyrrolidone |
| KR101398936B1 (en) * | 2012-04-05 | 2014-05-27 | 성균관대학교산학협력단 | Method for polyamide resin |
| US10138344B2 (en) * | 2015-03-19 | 2018-11-27 | Ricoh Company, Ltd. | Particulate polyamide, and method for preparing the particulate polyamide |
-
2018
- 2018-09-27 CN CN201880063591.3A patent/CN111164130A/en active Pending
- 2018-09-27 US US16/651,075 patent/US20200262976A1/en not_active Abandoned
- 2018-09-27 WO PCT/JP2018/036109 patent/WO2019069799A1/en unknown
- 2018-09-27 KR KR1020207005910A patent/KR102292169B1/en active IP Right Grant
- 2018-09-27 EP EP18864184.9A patent/EP3693405A4/en active Pending
- 2018-09-27 JP JP2019546670A patent/JP6851496B2/en active Active
- 2018-10-01 TW TW107134687A patent/TWI705985B/en not_active IP Right Cessation
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS376746B1 (en) | 1960-04-05 | 1962-07-02 | ||
| JPH0472329A (en) * | 1990-07-12 | 1992-03-06 | Shinto Paint Co Ltd | Production of polyamide resin powder |
| JPH0539355A (en) | 1991-08-06 | 1993-02-19 | Ube Ind Ltd | Production of powdered 2-pyrrolidone polymer |
| JPH05295108A (en) * | 1992-04-14 | 1993-11-09 | Ube Ind Ltd | Production of high-purity 2-pyrrolidone polymer |
| JPH06322109A (en) * | 1993-05-07 | 1994-11-22 | Kuraray Co Ltd | Synthesis of polyamide |
| JPH07316288A (en) * | 1994-05-30 | 1995-12-05 | Unitika Ltd | Method of polymerizing epsilon-caprolactam |
| JP2009155608A (en) * | 2007-12-28 | 2009-07-16 | National Institute Of Advanced Industrial & Technology | Polyamide 4 copolymer introducing branch structure, and its producing method |
| JP2016186068A (en) | 2015-03-19 | 2016-10-27 | 株式会社リコー | Polyamide particle and production method thereof |
| JP2017193534A (en) | 2016-03-31 | 2017-10-26 | 株式会社松風 | Lithium silicate glass composition free of al2o3 |
Non-Patent Citations (2)
| Title |
|---|
| RODA, J. ET AL.: "Polymerization of lactams, 37a, Isolation and Characterization of Clkali Carboxylates of 2-Pyrrolidone", MAKROMOL. CHEM., RAPID COMMUN., vol. 1, 1980, pages 165 - 169, XP055591846 * |
| See also references of EP3693405A4 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021095749A1 (en) * | 2019-11-11 | 2021-05-20 | 株式会社クレハ | Polyamide particles and method for manufacturing the same |
| WO2022113993A1 (en) | 2020-11-30 | 2022-06-02 | 東レ株式会社 | Fine polyamide particles and production method therefor |
| KR20230112617A (en) | 2020-11-30 | 2023-07-27 | 도레이 카부시키가이샤 | Polyamide microparticles and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111164130A (en) | 2020-05-15 |
| KR20200032199A (en) | 2020-03-25 |
| JP6851496B2 (en) | 2021-03-31 |
| US20200262976A1 (en) | 2020-08-20 |
| TW201922843A (en) | 2019-06-16 |
| JPWO2019069799A1 (en) | 2020-10-22 |
| KR102292169B1 (en) | 2021-08-20 |
| EP3693405A1 (en) | 2020-08-12 |
| EP3693405A4 (en) | 2021-06-09 |
| TWI705985B (en) | 2020-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100945632B1 (en) | Synthesis of MDH-polymer hybrid paticles | |
| Jia et al. | Atom transfer radical polymerization in microemulsion | |
| JPH0723433B2 (en) | Curing agent for monomer adhesive | |
| WO2019069799A1 (en) | Production method for polyamide-4 particles | |
| Hong et al. | Polyelectrolyte-assisted synthesis of polystyrene microspheres by dispersion polymerization and the subsequent formation of silica shell | |
| JP2017515931A (en) | Control of controlled radical polymerization of acrylates by light | |
| Abraham et al. | Synthesis of poly (styrene‐block‐tert‐butyl acrylate) star polymers by atom transfer radical polymerization and micellization of their hydrolyzed polymers | |
| CN104371082B (en) | A kind of preparation method of polylactic acid composition | |
| JP4969166B2 (en) | Amphiphilic triblock copolymer composed of poly (2-vinylpyridine) block and poly (alkylisocyanate) block and polymerization method thereof | |
| Hosseinzadeh | Sorption of lead ion from aqueous solution by carboxylic acid groups containing adsorbent polymer | |
| JP5101816B2 (en) | Hyperbranched polymer | |
| JP6815247B2 (en) | Polyamide manufacturing method | |
| Khezri et al. | Activators regenerated by electron transfer for atom transfer radical polymerization of styrene in the presence of hydrophobically modified silica aerogel nanoparticles | |
| JP3167418B2 (en) | Solid catalyst component for ultra high molecular weight polyethylene production | |
| Zhang et al. | Tunable Shell Thickness in Silica Nanospheres Functionalized by a Hydrophobic PMMA‐PSt Diblock Copolymer Brush via Activators Generated by Electron Transfer for Atom Transfer Radical Polymerization | |
| JP5652757B2 (en) | 1-methyleneindane polymer and production method thereof, block copolymer and production method thereof, and optical film. | |
| Pizarro et al. | Synthesis of functional poly (styrene)‐block‐(methyl methacrylate/methacrylic acid) by homogeneous reverse atom transfer radical polymerization: Spherical nanoparticles, thermal behavior, self‐aggregation, and morphological properties | |
| JPH0873602A (en) | Production of polyamide powder | |
| Liu et al. | A facile strategy for the functionalization of poly [cyclotriphosphazene‐co‐(4, 4′‐sulfonyldiphenol)] materials | |
| CN102336877B (en) | Method for preparing high polymer and high polymer nano-particles through polymerization in aqueous dispersed phase | |
| JPH11343303A (en) | Production of polyvinyl ether and catalyst used for its production | |
| JP3386856B2 (en) | Method for producing powdery polyimide precursor | |
| JPH06322109A (en) | Synthesis of polyamide | |
| Kohri et al. | A green approach for the synthesis of fluorescent polymer particles by combined use of enzymatic miniemulsion polymerization with clickable surfmer and click reaction | |
| Growney | Use of Commercial Block Copolymers as Soot Dispersants in Engine Oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18864184 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 20207005910 Country of ref document: KR Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 2019546670 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2018864184 Country of ref document: EP Effective date: 20200504 |